Présentation

In the last years important progress has been made on long-standing fundamental questions such as those related to sound properties in glasses and their relation with the universal low-temperature anomalies. A comprehensive picture of the nontrivial frequency dependence of sound attenuation in oxide glasses can now be proposed. It is controlled by three processes which in increasing order of the frequency at which they dominate are : the thermal relaxation of defects, relaxation via anharmonic interactions with the thermal bath, and a remarkably rapid increase (α Ω4) towards a Ioffe-Regel crossover at THz frequencies which we have evidenced in two oxide glasses. The latter mechanism relates to the boson peak and the low temperature plateau generally observed in the thermal conductivity. The close relation between the Ioffe-Regel crossover and the boson peak implies a resonance of these rather local low-lying optic modes with acoustic modes near the Ioffe-Regel limit.

A large body of experimental work on the microstructure and dynamics of simplifiedindustrial nanocomposites made of disordered silica filler in a styrene-butadiene matrixby solid-phase mixing is regrouped and critically discussed in this feature article. Recentresults encompass systems with varying polymer mass, grafting functionality, and fillercontent. They have been obtained by simulation-based structural modelling of nanoparticleaggregate size and mass deduced from small-angle scattering and transmission electronmicroscopy. Our model has been validated by independent swelling experiments.Comparison of structurally-close nanocomposites of widely different chain mass led tothe identification of a unique structure-determining parameter, the grafting density, aswell as to a unified picture of aggregate formation mechanisms in complex nanocompositesduring mixing. In addition, low-field proton NMR allowed for the characterization ofdynamically slowed-down (‘glassy’) polymer layers, which were shown not to dominatethe rheological response, unlike the structural contribution. Finally, broadband dielectricspectroscopy was used in an innovative manner to identify filler percolation – also identifiedby rheology – via dynamics along filler surfaces.

We discuss two procedures to obtain empirical potentials from ab initio trajectories. The first methodconsists in adjusting the parameters of an empirical pair potential so that the radial distribution functionsextracted from classical simulations using this potential match the ones extracted from the ab initio sim-ulations. As a case study, we consider the example of amorphous silica, a material that is highly relevantin the field of glass science as well as in geology. With our approach we are able to obtain an empiricalpotential that gives a better description with respect to structural and thermodynamic properties thanthe potential proposed by van Beest, Kramer, and van Santen, and that has been very frequently usedas a model for amorphous silica. The second method is the so-called ‘‘force matching” approach proposedby Ercolessi and Adams to obtain an empirical potential. We demonstrate that for the case of silica thismethod does not yield a reliable potential and discuss the likely origin for this failure.

The fluctuations of electric polarization in a disordered ferroelectric substance, relaxor crystalPbMg1/3Nb2/3O3 (PMN), were studied using a nonlinear inelastic light-scattering technique, hyper-Raman scattering, within a 5–100 cm−1 spectral interval and in a broad temperature range from 20 to900 K. The split ferroelectric mode reveals a local anisotropy of up to about 400 K. Spectral anomaliesobserved at higher temperatures are explained as due to avoided crossing of the single primary polar softmode with a temperature-independent, nonpolar spectral feature near 45 cm−1, known from Ramanscattering. The temperature changes of the vibrational modes involved in the measured fluctuation spectraof PMN were captured in a simple model that accounts for the temperature dependence of the dielectricpermittivity as well. The observed slowing down of the relaxational dynamics directly correlates with thehuge increase of the dielectric permittivity.

In the forthcoming ecological era, new European environmental regulations (horizon 2020) will impose the design of new “green” materials with lower energetic production costs. In this context, the (...)